US20060147711A1 - Aramid cord treatment - Google Patents

Aramid cord treatment Download PDF

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Publication number
US20060147711A1
US20060147711A1 US11/148,839 US14883905A US2006147711A1 US 20060147711 A1 US20060147711 A1 US 20060147711A1 US 14883905 A US14883905 A US 14883905A US 2006147711 A1 US2006147711 A1 US 2006147711A1
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Prior art keywords
elastomer
composition
amount
aramid fiber
fiber cord
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Granted
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US11/148,839
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US8211502B2 (en
Inventor
Ramon DiMascio
Robert Schisler
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ContiTech USA Inc
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Goodyear Tire and Rubber Co
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Priority to US11/148,839 priority Critical patent/US8211502B2/en
Application filed by Goodyear Tire and Rubber Co filed Critical Goodyear Tire and Rubber Co
Publication of US20060147711A1 publication Critical patent/US20060147711A1/en
Assigned to VEYANCE TECHNOLOGIES, INC. reassignment VEYANCE TECHNOLOGIES, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: THE GOODYEAR TIRE & RUBBER COMPANY
Assigned to JPMORGAN CHASE BANK, N.A. reassignment JPMORGAN CHASE BANK, N.A. SECURITY AGREEMENT Assignors: VEYANCE TECHNOLOGIES, INC.
Assigned to LEHMAN COMMERCIAL PAPER INC., AS COLLATERAL AGENT reassignment LEHMAN COMMERCIAL PAPER INC., AS COLLATERAL AGENT SECURITY AGREEMENT Assignors: VEYANCE TECHNOLOGIES, INC.
Assigned to THE GOODYEAR TIRE & RUBBER COMPANY reassignment THE GOODYEAR TIRE & RUBBER COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DIMASCIO, RAMON JOSEPH, II, SCHISLER, ROBERT CHARLES
Priority to US13/478,781 priority patent/US20120231193A1/en
Publication of US8211502B2 publication Critical patent/US8211502B2/en
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Assigned to VEYANCE TECHNOLOGIES, INC. reassignment VEYANCE TECHNOLOGIES, INC. RELEASE OF SECURITY INTEREST AT REEL/FRAME 20035/0550 Assignors: JPMORGAN CHASE BANK, N.A.
Assigned to VEYANCE TECHNOLOGIES, INC. reassignment VEYANCE TECHNOLOGIES, INC. RELEASE OF SECURITY INTEREST AT REEL/FRAME 20035/0484 Assignors: BARCLAYS BANK PLC
Assigned to CONTITECH USA, INC. reassignment CONTITECH USA, INC. CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: VEYANCE TECHNOLOGIES, INC
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/55—Epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
    • B29B15/08—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of reinforcements or fillers
    • B29B15/10—Coating or impregnating independently of the moulding or shaping step
    • B29B15/12—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length
    • B29B15/122—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length with a matrix in liquid form, e.g. as melt, solution or latex
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2063/00—Use of EP, i.e. epoxy resins or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
    • B29K2077/10—Aromatic polyamides [polyaramides] or derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/08—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of continuous length, e.g. cords, rovings, mats, fabrics, strands or yarns
    • B29K2105/10—Cords, strands or rovings, e.g. oriented cords, strands or rovings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2313/00—Use of textile products or fabrics as reinforcement
    • B29K2313/02—Use of textile products or fabrics as reinforcement coated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino carboxylic acids or of polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/34—Polyamides
    • D06M2101/36—Aromatic polyamides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/1386—Natural or synthetic rubber or rubber-like compound containing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
    • Y10T428/249933—Fiber embedded in or on the surface of a natural or synthetic rubber matrix
    • Y10T428/249937—Fiber is precoated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core

Definitions

  • This invention relates to the treatment of textile cords for use as tensile reinforcements in elastomeric products, and more particularly, to the treatment of aramid cords for such uses.
  • Textile cord has long been used as a tensile reinforcement material for reinforcing various elastomeric products, for example, power transmission belts, conveyor belts, hoses, tires, and the like.
  • the textile cord typically is embedded in the particular elastomeric material.
  • the cord is treated prior to being embedded in the elastomer in order to enhance any of a number of desired properties, for example, cord-to-elastomer adhesion, inhibition of textile-filament degradation, and flexibility.
  • aramid cord that is to be used in reinforcing an elastomeric product (i.e., a rubber product).
  • one treatment proposes treating the cord with a resorcinol-formalin-rubber latex adhesive (“RFL”) liquid.
  • RFL resorcinol-formalin-rubber latex adhesive
  • the bending performance of cords treated with RFL solutions is good, there is a tendency for cut edges to fray during manufacturing and belt operation.
  • moisture uptake can be a problem due to incomplete impregnation of the cord due to the evaporation of the water carrier which can lead to voids and untreated areas of cord.
  • Moisture uptake has the potential to lead to dimensional instability in certain types of fibers like aramid.
  • Another approach calls for pretreating the cord with an isocyanate solution or an aqueous based epoxy solution, and then treating the pretreated cord with an RFL liquid. While this methodology tends to improve a cord's resistance to fray, it results in an undesirable reduction in bending fatigue resistance. Epoxy solutions and isocyanate solutions may also lead to unwanted moisture uptake after treatment.
  • the present invention addresses the limitations and drawbacks described above by employing select combinations of component materials that are 100% reactive.
  • the treatment compositions and methods of the invention result in improved cord penetration and treatment uniformity, including fewer treatment voids.
  • the compositions and methods also result in treated aramid cord that has improved dimensional stability, moisture retardation, fray resistance, and cuttability. This is accomplished by providing a treatment composition and method that include a bisphenol-A-based- and/or bisphenol-F-based-liquid epoxy resin, a reactive diluent, and a curing agent.
  • the composition and method also may include an elastomer-modified epoxy-functional adduct and/or an elastomer-modified epoxy-resin adduct.
  • the term “phr” means parts by weight per hundred parts by weight of resin.
  • resin as used in the definition of phr above, means the liquid epoxy resin and, if used, the reactive diluent, the elastomer-modified epoxy-functional adduct, and the elastomer-modified epoxy-resin adduct.
  • aramid fiber cord and “aramid cord” refer to cord in which at least one of the fibers, or threads, is an aramid (i.e., a highly aromatic polyamide).
  • the treatment composition of the invention may include a bisphenol-A-based- and/or a bisphenol-F-based-liquid epoxy resin, a reactive diluent, and a curing agent. If desired, the treatment composition also may include an elastomer-modified epoxy-functional adduct and/or an elastomer modified epoxy-resin adduct.
  • the liquid epoxy resin may be one or more bisphenol-A-based liquid epoxy resins, one or more bisphenol-F-based liquid epoxy resins, or combinations thereof.
  • a bisphenol-A/epichlorohydrin-derived liquid epoxy resin include EPONTM Resin 828 from Resolution Performance Products LLC of Houston, Tex., and D.E.R. 331 from The Dow Chemical Company of Midland, Mich.
  • An example of a bisphenol-F/epichlorohydrin-derived epoxy resin is EPONTM Resin 863 from Resolution Performance Products LLC.
  • the liquid epoxy resin or resins may be present in an amount of from about 40 to about 90 phr, advantageously from about 60 to about 80 phr.
  • the curing-agent component for use in forming the cord-treatment composition may include one or more polyamides, polyamines, and/or amidoamines.
  • polyamides include Ancamide® 910 from Air Products and Chemicals, Inc. of Allentown, Pa. and EPI-CURETM Curing Agent 3140 from Resolution Performance Products LLC.
  • An example of a suitable polyamine is EPI-CURETM Curing Agent 3164 from Resolution Performance Products LLC.
  • amidoamines include EPI-CURETM Curing Agent 3010, 3055, and 3061, all from Resolution Performance Products LLC, and AncamideTM 2447 from Air Products and Chemicals, Inc.
  • the curing agent or agents may be present in an amount of from about 0.6 to about 1.5 times the stoichiometric quantity, as determined using the amine-H-equivalent-weight (AHEW)/epoxide equivalent weight (EEW) method, advantageously from about 0.7 to about 1 times the stoichiometric quantity.
  • AHEW/EEW method is described: (1) in an Air Products document entitled Calculating Stoichiometry Ratios for Epoxy Curing Agents and Resins, further identified by the notice “ ⁇ Air Products and Chemicals, Inc., 2003 (23202)”; and (2) on page 7 of a Dow Chemical document entitled Dow Liquid Epoxy Resins published January 1999 (Form No. 296-00224-0199 WC+M). Both of these documents are incorporated into this patent document by reference.
  • the reactive diluent may be one or more glycidyl ethers, one or more glycidyl esters, or a combination thereof.
  • ethers include butyl glycidyl ether, cresyl glycidyl ether, 2-ethylhexyl glycidyl ether, a polyglycidyl ether of an aliphatic polyol, and a polyglycidyl ether of acstor oil.
  • An example of a glycidyl ester is a glycidyl ester of a synthetic saturated monocarboxylic acid.
  • glycidyl ethers examples include HELOXYTM Modifier 8 and Modifier 116 from Resolution Performance Products LLC, as well as Epodile® 746 and 748 from Air Products and Chemicals, Inc.
  • An example of a particular glycidyl ester is CARDURATM Resin E-1OP from Resolution Performance Products LLC.
  • the reactive diluent or diluents may be present in an amount from about 0 to about 40 phr, advantageously from about 10 to about 30 phr.
  • a composition or compositions of one or more liquid epoxy resins that already have been combined with one or more reactive diluents may be used—either in place of, or in addition to, one or more separate liquid epoxy resins and reactive diluents.
  • diluent-modified liquid epoxy resins include EPONTM Resin 8132 (a bisphenol-A-based epoxy resin diluted with an alkyl glycidyl ether) from Resolution Performance Products LLC, D.E.R. 324 (a C 12 -C 14 aliphatic-chain-glycidyl-ether-modified bisphenol-A-based liquid epoxy resin) from The Dow Chemical Company, and D.E.R. 353 (a C 12 -C 14 aliphatic-chain-glycidyl-ether-modified bisphenol-A/F-based liquid epoxy resin) also from The Dow Chemical Company.
  • one or more elastomer-modified epoxy-functional adducts and/or elastomer-modified epoxy-resin adducts also may be used to form the cord-treatment composition.
  • elastomer-modified epoxy-functional adducts include a reaction product of a diglycidyl ether of neopentyl alcohol and a carboxyl-terminated butadiene-acrylonitrile elastomer (e.g., EPONTM Resin 58034 from Resolution Performance Products LLC), a reaction product of a diglycidyl ether of bisphenol-A and a carboxyl-terminated butadiene-acrylonitrile elastomer (e.g., EPONTM Resin 58006 from Resolution Performance Products LLC), a carboxyl-terminated butadiene-acrylonitrile elastomer (e.g., CTBN-1300X8 and CTBN-1300X13 from Noveon, Inc.
  • an amine-terminated butadiene-acrylonitrile elastomer e.g., ATBN-1300X16 and ATBN-1300X42 from Noveon, Inc.
  • An example of the elastomer-modified epoxy-resin adduct is an adduct of a bisphenol-F-based epoxy resin and a carboxyl-terminated butadiene-acrylonitrile elastomer (e.g., EPONTM Resin 58003 from Resolution Performance Products LLC).
  • the adduct or adducts may be present in an amount of from about 0 to about 30 phr, advantageously from about 10 to about 25 phr.
  • the treatment compositions may be made using any suitable method(s) and equipment.
  • the components of the treatment composition may be mixed in an appropriately-sized steel tank, bucket, or drum at room temperature.
  • the component materials may be added in any order. For example, if a liquid epoxy resin, a reactive diluent, an elastomer-modified adduct, and a curing agent are used, the resin and diluent may be mixed together, followed by the addition and mixing of the adduct, followed by the addition and mixing of the curing agent.
  • the aramid cord is heated before being treated with the particular treatment composition.
  • Any suitable heating method and apparatus may be used, for example, a drying chamber or an oven.
  • the cord may be heated at a temperature of from about 110 to about 120° C. for a period of about 12 to about 24 hours.
  • the heated cord then may be treated with the composition using any suitable method(s) and equipment.
  • the cord may be treated using a conventional large-scale dip-unit assembly or a conventional pultrusion assembly.
  • any excess treatment composition may be removed from the cord using any conventional technique.
  • excess composition may be wiped off of the treated cord.
  • the treated cord may be pulled through an orifice, with the orifice size advantageously determined based on the cord dimensions and the desired epoxy retention level.
  • the cord then may be dried in a suitable oven or drying chamber at a temperature of from about 100 to about 150° C. for a period of from about 10 to about 30 minutes.
  • any suitable product or products then may be made using the treated aramid cord, according to the particular manufacturing technique(s) for each such product, as is known to those of ordinary skill in the art.
  • rubber-based products that may include the treated aramid cord are power transmission belt components, power transmission belts, tire components, tires, hose components, hoses, conveyor belt components, conveyor belts, and rubber containers.
  • Kevlar® aramid cord Lengths of Kevlar® aramid cord were treated and tested as described below.
  • Control samples (designated by the Letter “A” in Tables I and II) were prepared by treating lengths of Kevlar® cord using the ingredients and amounts listed in Table I, under the Sample A heading.
  • the treatment included two main steps, as follows. In the first treatment step, lengths of Kevlar® cord were treated with an aqueous dispersion containing about 5% by weight of polyamide and about 1% epoxy, as indicated in Table I. In the second treatment step, the lengths of polyamide/epoxy treated cord were further treated with an RFL liquid.
  • test samples were prepared by treating lengths of Kevlar® cord with one of the treatment compositions identified under the B through H headings in Table I.
  • Each of the treatment compositions was prepared by weighing out, combining, and mixing the particular ingredients in a 200 ml lab beaker at room temperature.
  • the corresponding lengths of aramid cord Prior to contact with a particular treatment composition, the corresponding lengths of aramid cord were heated at a temperature of about 107° C. for about 24 hours.
  • the heated lengths of aramid cord then were hand-dipped into the particular treatment composition, pulled through a rubber orifice having a 2 mm diameter, and hand-wiped with a clean paper napkin to remove excess composition.
  • the treated lengths of cord then were heated in a drying oven at about 150° C. for about 8 minutes, thereby curing the treatment composition.
  • the adhesion test was performed using an H-block method, substantially as described in ASTM D 4776-98.
  • the epoxy/HNBR interaction test was performed by visually inspecting the treated cord once it had been pulled out of the H-block.
  • the test results represent a visual observation of rubber coverage on the cord surface.
  • the numeral 1 represents about 0% rubber coverage
  • 2 represents about 50% rubber coverage
  • 3 represents more than about 90% rubber coverage on the cord surface.
  • Treated cord flexibility was measured by visual observation. Specifically, each treated cord was bent around a cylindrical fixture having a diameter of about one inch, and a visual observation was made of the amount of cracking, if any, of the treatment composition on the cord.
  • the numeral 1 indicates that a sample showed no visual cracking and was highly flexible, 2 represents some visual cracking and a moderate degree of flexibility, and 3 represents a high level of cracking and relative inflexibility or stiffness.

Abstract

A composition and method for treating an aramid cord include a bisphenol-A-based- and/or a bisphenol-F-based-liquid epoxy resin, a reactive diluent, and a curing agent. The composition and method also may include an elastomer-modified epoxy-functional adduct and/or an elastomer-modified epoxy-resin adduct.

Description

    CROSS-REFERENCE TO RELATED APPLICATION
  • This patent document claims the benefit of the filing date of Provisional U.S. Patent Application No. 60/640,816 entitled “Aramid Cord Treatment” and filed on Dec. 30, 2004. The entire disclosure of Provisional U.S. Patent Application No. 60/640,816 is incorporated into this patent document by reference.
    • BACKGROUND OF THE INVENTION
  • 1. Field of the Invention
  • This invention relates to the treatment of textile cords for use as tensile reinforcements in elastomeric products, and more particularly, to the treatment of aramid cords for such uses.
  • 2. Description of Related Art
  • Textile cord has long been used as a tensile reinforcement material for reinforcing various elastomeric products, for example, power transmission belts, conveyor belts, hoses, tires, and the like. In order to serve as a reinforcement, the textile cord typically is embedded in the particular elastomeric material. And, depending on the particular end use of the reinforced elastomer, oftentimes the cord is treated prior to being embedded in the elastomer in order to enhance any of a number of desired properties, for example, cord-to-elastomer adhesion, inhibition of textile-filament degradation, and flexibility.
  • Various treatments have been proposed for treating aramid cord that is to be used in reinforcing an elastomeric product (i.e., a rubber product). Specifically, one treatment proposes treating the cord with a resorcinol-formalin-rubber latex adhesive (“RFL”) liquid. While the bending performance of cords treated with RFL solutions is good, there is a tendency for cut edges to fray during manufacturing and belt operation. In addition, moisture uptake can be a problem due to incomplete impregnation of the cord due to the evaporation of the water carrier which can lead to voids and untreated areas of cord. Moisture uptake has the potential to lead to dimensional instability in certain types of fibers like aramid. Another approach calls for pretreating the cord with an isocyanate solution or an aqueous based epoxy solution, and then treating the pretreated cord with an RFL liquid. While this methodology tends to improve a cord's resistance to fray, it results in an undesirable reduction in bending fatigue resistance. Epoxy solutions and isocyanate solutions may also lead to unwanted moisture uptake after treatment.
    • SUMMARY OF THE INVENTION
  • The present invention addresses the limitations and drawbacks described above by employing select combinations of component materials that are 100% reactive. The treatment compositions and methods of the invention result in improved cord penetration and treatment uniformity, including fewer treatment voids. The compositions and methods also result in treated aramid cord that has improved dimensional stability, moisture retardation, fray resistance, and cuttability. This is accomplished by providing a treatment composition and method that include a bisphenol-A-based- and/or bisphenol-F-based-liquid epoxy resin, a reactive diluent, and a curing agent. The composition and method also may include an elastomer-modified epoxy-functional adduct and/or an elastomer-modified epoxy-resin adduct.
    • DETAILED DESCRIPTION OF EMBODIMENTS OF THE INVENTION
  • As used herein, the term “phr” means parts by weight per hundred parts by weight of resin. The term “resin”, as used in the definition of phr above, means the liquid epoxy resin and, if used, the reactive diluent, the elastomer-modified epoxy-functional adduct, and the elastomer-modified epoxy-resin adduct. In addition, as used herein, the terms “aramid fiber cord” and “aramid cord” refer to cord in which at least one of the fibers, or threads, is an aramid (i.e., a highly aromatic polyamide).
  • The treatment composition of the invention may include a bisphenol-A-based- and/or a bisphenol-F-based-liquid epoxy resin, a reactive diluent, and a curing agent. If desired, the treatment composition also may include an elastomer-modified epoxy-functional adduct and/or an elastomer modified epoxy-resin adduct.
  • The liquid epoxy resin may be one or more bisphenol-A-based liquid epoxy resins, one or more bisphenol-F-based liquid epoxy resins, or combinations thereof. Examples of a bisphenol-A/epichlorohydrin-derived liquid epoxy resin include EPON™ Resin 828 from Resolution Performance Products LLC of Houston, Tex., and D.E.R. 331 from The Dow Chemical Company of Midland, Mich. An example of a bisphenol-F/epichlorohydrin-derived epoxy resin is EPON™ Resin 863 from Resolution Performance Products LLC. If desired, the liquid epoxy resin or resins may be present in an amount of from about 40 to about 90 phr, advantageously from about 60 to about 80 phr.
  • The curing-agent component for use in forming the cord-treatment composition may include one or more polyamides, polyamines, and/or amidoamines. Examples of such polyamides include Ancamide® 910 from Air Products and Chemicals, Inc. of Allentown, Pa. and EPI-CURE™ Curing Agent 3140 from Resolution Performance Products LLC. An example of a suitable polyamine is EPI-CURE™ Curing Agent 3164 from Resolution Performance Products LLC. And examples of such amidoamines include EPI-CURE™ Curing Agent 3010, 3055, and 3061, all from Resolution Performance Products LLC, and Ancamide™ 2447 from Air Products and Chemicals, Inc. If desired, the curing agent or agents may be present in an amount of from about 0.6 to about 1.5 times the stoichiometric quantity, as determined using the amine-H-equivalent-weight (AHEW)/epoxide equivalent weight (EEW) method, advantageously from about 0.7 to about 1 times the stoichiometric quantity. The AHEW/EEW method is described: (1) in an Air Products document entitled Calculating Stoichiometry Ratios for Epoxy Curing Agents and Resins, further identified by the notice “©Air Products and Chemicals, Inc., 2003 (23202)”; and (2) on page 7 of a Dow Chemical document entitled Dow Liquid Epoxy Resins published January 1999 (Form No. 296-00224-0199 WC+M). Both of these documents are incorporated into this patent document by reference.
  • In embodiments of the invention that include a reactive diluent, the reactive diluent may be one or more glycidyl ethers, one or more glycidyl esters, or a combination thereof. Examples of such ethers include butyl glycidyl ether, cresyl glycidyl ether, 2-ethylhexyl glycidyl ether, a polyglycidyl ether of an aliphatic polyol, and a polyglycidyl ether of acstor oil. An example of a glycidyl ester is a glycidyl ester of a synthetic saturated monocarboxylic acid. Examples of specific glycidyl ethers include HELOXY™ Modifier 8 and Modifier 116 from Resolution Performance Products LLC, as well as Epodile® 746 and 748 from Air Products and Chemicals, Inc. An example of a particular glycidyl ester is CARDURA™ Resin E-1OP from Resolution Performance Products LLC. If desired, the reactive diluent or diluents may be present in an amount from about 0 to about 40 phr, advantageously from about 10 to about 30 phr.
  • If desired, a composition or compositions of one or more liquid epoxy resins that already have been combined with one or more reactive diluents may be used—either in place of, or in addition to, one or more separate liquid epoxy resins and reactive diluents. Examples of such diluent-modified liquid epoxy resins include EPON™ Resin 8132 (a bisphenol-A-based epoxy resin diluted with an alkyl glycidyl ether) from Resolution Performance Products LLC, D.E.R. 324 (a C12-C14 aliphatic-chain-glycidyl-ether-modified bisphenol-A-based liquid epoxy resin) from The Dow Chemical Company, and D.E.R. 353 (a C12-C14 aliphatic-chain-glycidyl-ether-modified bisphenol-A/F-based liquid epoxy resin) also from The Dow Chemical Company.
  • If desired, one or more elastomer-modified epoxy-functional adducts and/or elastomer-modified epoxy-resin adducts also may be used to form the cord-treatment composition. Examples of elastomer-modified epoxy-functional adducts include a reaction product of a diglycidyl ether of neopentyl alcohol and a carboxyl-terminated butadiene-acrylonitrile elastomer (e.g., EPON™ Resin 58034 from Resolution Performance Products LLC), a reaction product of a diglycidyl ether of bisphenol-A and a carboxyl-terminated butadiene-acrylonitrile elastomer (e.g., EPON™ Resin 58006 from Resolution Performance Products LLC), a carboxyl-terminated butadiene-acrylonitrile elastomer (e.g., CTBN-1300X8 and CTBN-1300X13 from Noveon, Inc. of Cleveland, Ohio), and an amine-terminated butadiene-acrylonitrile elastomer (e.g., ATBN-1300X16 and ATBN-1300X42 from Noveon, Inc.). An example of the elastomer-modified epoxy-resin adduct is an adduct of a bisphenol-F-based epoxy resin and a carboxyl-terminated butadiene-acrylonitrile elastomer (e.g., EPON™ Resin 58003 from Resolution Performance Products LLC). If desired, the adduct or adducts may be present in an amount of from about 0 to about 30 phr, advantageously from about 10 to about 25 phr.
  • The treatment compositions may be made using any suitable method(s) and equipment. For example, the components of the treatment composition may be mixed in an appropriately-sized steel tank, bucket, or drum at room temperature. In addition, the component materials may be added in any order. For example, if a liquid epoxy resin, a reactive diluent, an elastomer-modified adduct, and a curing agent are used, the resin and diluent may be mixed together, followed by the addition and mixing of the adduct, followed by the addition and mixing of the curing agent.
  • Advantageously, the aramid cord is heated before being treated with the particular treatment composition. Any suitable heating method and apparatus may be used, for example, a drying chamber or an oven. The cord may be heated at a temperature of from about 110 to about 120° C. for a period of about 12 to about 24 hours.
  • The heated cord then may be treated with the composition using any suitable method(s) and equipment. For example, the cord may be treated using a conventional large-scale dip-unit assembly or a conventional pultrusion assembly. Then, if needed, any excess treatment composition may be removed from the cord using any conventional technique. For example, excess composition may be wiped off of the treated cord. Or the treated cord may be pulled through an orifice, with the orifice size advantageously determined based on the cord dimensions and the desired epoxy retention level. The cord then may be dried in a suitable oven or drying chamber at a temperature of from about 100 to about 150° C. for a period of from about 10 to about 30 minutes.
  • Any suitable product or products then may be made using the treated aramid cord, according to the particular manufacturing technique(s) for each such product, as is known to those of ordinary skill in the art. Examples of rubber-based products that may include the treated aramid cord are power transmission belt components, power transmission belts, tire components, tires, hose components, hoses, conveyor belt components, conveyor belts, and rubber containers.
    • EXAMPLE
  • Lengths of Kevlar® aramid cord were treated and tested as described below.
  • Control samples (designated by the Letter “A” in Tables I and II) were prepared by treating lengths of Kevlar® cord using the ingredients and amounts listed in Table I, under the Sample A heading. The treatment included two main steps, as follows. In the first treatment step, lengths of Kevlar® cord were treated with an aqueous dispersion containing about 5% by weight of polyamide and about 1% epoxy, as indicated in Table I. In the second treatment step, the lengths of polyamide/epoxy treated cord were further treated with an RFL liquid.
  • Other test samples (designated by the letters “B” through “H” in Tables I and II) were prepared by treating lengths of Kevlar® cord with one of the treatment compositions identified under the B through H headings in Table I. Each of the treatment compositions was prepared by weighing out, combining, and mixing the particular ingredients in a 200 ml lab beaker at room temperature. Prior to contact with a particular treatment composition, the corresponding lengths of aramid cord were heated at a temperature of about 107° C. for about 24 hours. The heated lengths of aramid cord then were hand-dipped into the particular treatment composition, pulled through a rubber orifice having a 2 mm diameter, and hand-wiped with a clean paper napkin to remove excess composition. The treated lengths of cord then were heated in a drying oven at about 150° C. for about 8 minutes, thereby curing the treatment composition.
  • A few of the treated cords resulting from each of the eight (A through H) different treatments then were partially embedded, each in their own respective block of hydrogenated nitrile rubber (“HNBR”). Each block subsequently was cured at about 170° C. for about 20 minutes, in preparation for performing the adhesion, interaction, and flexibility tests identified in Table II.
  • With reference to Table II, the adhesion test was performed using an H-block method, substantially as described in ASTM D 4776-98. The epoxy/HNBR interaction test was performed by visually inspecting the treated cord once it had been pulled out of the H-block. The test results represent a visual observation of rubber coverage on the cord surface. The numeral 1 represents about 0% rubber coverage, 2 represents about 50% rubber coverage, and 3 represents more than about 90% rubber coverage on the cord surface. Treated cord flexibility was measured by visual observation. Specifically, each treated cord was bent around a cylindrical fixture having a diameter of about one inch, and a visual observation was made of the amount of cracking, if any, of the treatment composition on the cord. For this particular test, the numeral 1 indicates that a sample showed no visual cracking and was highly flexible, 2 represents some visual cracking and a moderate degree of flexibility, and 3 represents a high level of cracking and relative inflexibility or stiffness.
  • All of the other tests performed and presented in Table II (max load, breaking strength, load at specified elongation (“LASE”), energy to break point, toughness, and modulus) were performed substantially in accordance with ASTM D 2256-97.
  • With reference to Table II, the lengths of Kevlar® aramid cord treated in accordance with the invention (resulting in Sample B-H treated cords) produced results generally comparable with those of the lengths of Kevlar® cord that received the control treatment (resulting in Sample A treated cords).
    TABLE I
    Samples
    A
    Description (Control) B C D E F G H
    Water 100
    Epoxy resin1 2.5
    Polyamide terpolymer (10 wt %), aq. 110
    dispersion2
    NaOH (30%) 0.1
    C12-C14 aliphatic chain glycidyl-ether-modified 80 80 80 80 80
    bisphenol-A-based liquid epoxy resin3
    C12-C14 aliphatic chain glycidyl-ether-modified 0 0 80 0
    bisphenol-A/F-based liquid epoxy resin4
    Bisphenol-A/epichlorohydrin-derived liquid 0 0 0 66.4
    epoxy resin5
    2-ethylhexyl glycidyl-ether6 20 0 20 20 5
    Alkyl C12-C14 glycidyl-ether7 0 0 0 33.6
    Adduct formed from reaction of diglycidyl 0 20 20 15
    ether of neopentyl glycol and CTBN rubber8
    ATBN reactive liquid copolymer9 25
    Aliphatic amidoamine10 0 25.1 19.5 19.93 18.55 0
    Oligomeric polyamine11 126.5 16.4 122 115
    Polyamide12 0 0 29 29.95 27.83 0

    1Denecol EX313 from Nagase Chemicals Ltd.

    2Genton 310 from General Plastics Corporation

    3D.E.R. 324 from The Dow Chemical Company

    4D.E.R. 353 from The Dow Chemical Company

    5EPON ™ Resin 828 from Resolution Performance Products LLC

    6HELOXY ™ Modifier 116 from Resolution Performance Products LLC

    7HELOXY ™ Modifier 8 from Resolution Performance Products LLC

    8EPON ™ Resin No. 58034 from Resolution Performance Products LLC

    9Hycar ® ATBN 1300X16 from Noveon, Inc.

    10EPI-CURE ™ Curing Agent No. 3061 from Resolution Performance Products LLC

    11EPI-CURE ™ Curing Agent No. 3164 from Resolution Performance Products LLC

    12Ancamide ® 910 from Air Products and Chemicals, Inc.
  • TABLE II
    Samples
    A
    Description (Control) B C D E F G H
    Adhesion, mean 713 352 635 793 650 674 391 240
    Epoxy/HNBR Interaction 3 1 3 2 2 2 1 1
    Flexibility 1 1.25 1.5 3 2 2 1.25 1.25
    Max. Load (N) 5,235 5,645 4,817 5,514 5,757 5,514 5,875 5,812
    Breaking Strength (N) 5,235 4,793 4,164 5,514 5,757 5,348 5,875 4,369
    LASE @ 1% (N) 309 786 224 297 417 506 824 739
    LASE @ 3% (N) 2,508 3,686 2,251 2,466 3,255 3,361 3,536 3,446
    LASE @ 5% (N) 3,666 1,248
    Energy to Break Pt (J) 27 28 26 35 28 26 31 32
    Toughness (Mpa) 27 26 16 36 22 20 28 32
    Modulus @ .05 & .1 of BRK 19,972 24,123 12,598 23,350 20,347 19,066 23,876 25,853
    (Mpa)
  • While the present invention has been illustrated by the description of embodiments, and while the illustrative embodiments have been described in considerable detail, it is not the intention of the inventors to restrict or in any way limit the scope of the appended claims to such detail. Additional advantages and modifications readily will appear to those skilled in the art. The invention in its broader aspects is therefore not limited to the specific details, representative apparatus and methods, and illustrative examples shown and described. Accordingly, departures may be made from such details without departing from the spirit or scope of the inventor's general inventive concept.

Claims (19)

1. A method of treating an aramid fiber cord, comprising the step of:
contacting the aramid fiber cord with a composition resulting from the combination of:
a liquid epoxy resin selected from the group consisting of a bisphenol-A-based liquid epoxy resin, a bisphenol-F-based liquid epoxy resin, and combinations thereof;
a reactive diluent; and
a curing agent,
thereby forming a treated aramid fiber cord, the treated aramid fiber cord including at least a portion of the composition.
2. The method of claim 1 wherein the composition is a solution.
3. The method of claim 1 wherein the liquid epoxy resin is present in an amount of from about 40 to about 90 phr.
4. The method of claim 1 wherein the liquid epoxy resin is present in an amount of from about 60 to about 80 phr.
5. The method of claim 1 wherein the reactive diluent is present in an amount of from about 0 to about 40 phr.
6. The method of claim 1 wherein the reactive diluent is present in an amount of from about 10 to about 30 phr.
7. The method of claim 1 wherein the reactive diluent is selected from the group consisting of a glycidyl ether, a glycidyl ester, and combinations thereof.
8. The method of claim 1 wherein the glycidyl ether is an aliphatic glycidyl ether.
9. The method of claim 1 wherein the curing agent is present in an amount of from about 0.6 to about 1.5 times the stoichiometric quantity, as determined using the amine-H-equivalent-weight (AHEW)/epoxide equivalent weight (EEW) method.
10. The method of claim 1 wherein the curing agent is present in an amount of from about 0.7 to about 1 times the stoichiometric quantity, as determined using the amine-H-equivalent-weight (AHEW)/epoxide equivalent weight (EEW) method.
11. The method of claim 1 wherein the curing agent is selected from the group consisting of a polyamide, a polyamine, an amidoamine, and combinations thereof.
12. The method of claim 1 wherein the composition further includes a component selected from the group consisting of an elastomer-modified epoxy-functional adduct, an elastomer-modified epoxy-resin adduct, and combinations thereof.
13. The method of claim 12 wherein: the elastomer-modified epoxy-functional adduct is selected from the group consisting of a reaction product of a diglycidyl ether of neopentyl alcohol and a carboxyl-terminated butadiene-acrylonitrile elastomer, a reaction product of a diglycidyl ether of bisphenol-A and a carboxyl-terminated butadiene-acrylonitrile elastomer, a carboxyl-terminated butadiene-acrylonitrile elastomer, an amine-terminated butadiene-acrylonitrile elastomer, and combinations thereof; and the elastomer-modified epoxy-resin adduct is an adduct of a bisphenol-F-based epoxy resin and a carboxyl-terminated butadiene-acrylonitrile elastomer.
14. The method of claim 1 further including the step of curing the portion of the composition.
15. The method of claim 1 wherein the treated aramid fiber cord includes an excess amount of the composition after the contacting step, the method further including the step of removing the excess amount of the composition.
16. The method of claim 15 wherein the treated aramid fiber cord includes a residual amount of the composition after the removing step, the method further including the step of curing the residual amount.
17. The method of claim 1 further including the step of heating the aramid fiber cord prior to the contacting step.
18. A rubber product comprising an aramid fiber cord treated according to the method of claim 1.
19. The rubber product of claim 18 wherein the rubber product is selected from the group consisting of a power transmission belt component, a power transmission belt, a tire component, a tire, a hose component, a hose, a conveyor belt, and a rubber container.
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US20120231193A1 (en) 2012-09-13

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